WO2013140991A1 - Method for producing olefin polymer - Google Patents

Abstract

[Problem] To provide a method for producing an olefin polymer having a high melting point and high molecular weight even under industrially feasible high-temperature conditions. [Solution] A method for producing an olefin polymer, characterized by comprising polymerizing a C₂ or higher olefin in the presence of an olefin-polymerizing catalyst, the catalyst including: (A) a cross-linked metallocene compound represented by general formula [1]; and (B) at least one species of compound selected from organoaluminumoxy compounds, organoaluminum compounds, and the like. (In formula [1], R¹-R⁴ represent hydrocarbon groups or the like; R⁵-R⁹ represent hydrogen atoms, halogen atoms, or the like; R¹⁰-R¹¹ represent hydrogen atoms or the like; R¹² represents a hydrocarbon group or the like; Y represents a carbon atom or the like; M represents Zr or the like; Y represents a carbon atom or the like; Q represents a halogen atom or the like; and j represents an integer 1-4.)

Description

Process for producing olefin polymer

The present invention relates to a method for producing an olefin polymer using an olefin polymerization catalyst containing a bridged metallocene compound having a specific structure, and particularly relates to a method for producing a high melting point and high molecular weight olefin polymer with high productivity. .

So-called metallocene compounds are well known as homogeneous catalysts for olefin polymerization. Regarding the method of polymerizing olefins using metallocene compounds (particularly the method of polymerizing α-olefins), W.W. Since the report of isotactic polymerization by Kaminsky et al., Many improvement studies have been conducted from the viewpoint of further improving stereoregularity and polymerization activity (Non-patent Document 1).

As a part of such research, as a result of polymerizing propylene in the presence of a specific catalyst, it is possible to obtain a polypropylene having a high tacticity such that the syndiotactic pentad fraction exceeds 0.7. A. Reported by Ewen (Non-Patent Document 2). Here, the specific catalyst includes a metallocene compound having a ligand obtained by crosslinking a cyclopentadienyl group and a fluorenyl group with isopropylidene, and an aluminoxane.

As an improvement of the metallocene compound, an attempt has been made to improve stereoregularity by changing the fluorenyl group to a 2,7-ditert-butylfluorenyl group (Patent Document 1). In addition, an attempt to improve stereoregularity by changing the fluorenyl group to a 3,6-ditert-butylfluorenyl group (Patent Document 2), or a combination of a cyclopentadienyl group and a fluorenyl group Attempts to improve stereoregularity by converting the cross-linked part (Patent Documents 3 and 4) have been reported.

On the other hand, as compared to dimethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene (3-tert-butyl-5-5-methylmethyl) introduced with a methyl group also at the 5-position of the cyclopentadienyl ring. It has also been reported that methylcyclopentadienyl) (fluorenyl) zirconium dichloride can obtain high molecular weight isotactic polypropylene (Patent Document 5).

Further, as a metallocene compound capable of polymerizing at a high temperature and capable of producing a high molecular weight polymer, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- (Butylfluorenyl) zirconium dichloride has also been reported (Patent Document 6).

As described above, an olefin polymer having a high melting point and a high molecular weight has been obtained by improving the metallocene compound, but the productivity is still not sufficient in an industrial production method. In particular, when these metallocene compounds are used by being dissolved in a hydrocarbon solvent, the solubility is not high, and it is necessary to use many solvents. In addition, the use of many solvents reduces the concentration of the catalyst solution composed of the metallocene compound, which reduces productivity due to the effects of poisoning and deactivation. For this reason, efficient production of an olefin polymer having a high melting point and a high molecular weight is desired.

Japanese Patent Laid-Open No. 04-069394 JP 2000-212194 A JP 2004-189666 A JP 2004-189667 A JP-T-2001-526730 JP 2007-302853 A

The problem to be solved by the present invention is to produce an olefin polymer having a high melting point and a high molecular weight by polymerizing an olefin such as propylene, which is advantageous in an industrial production method and has a high productivity. Is to provide.

The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using an olefin polymerization catalyst containing a crosslinked metallocene compound having a specific structure, and the present invention has been completed.

That is, the present invention relates to the following [1] to [12].
[1] (A) a bridged metallocene compound represented by the following general formula [1];
(B) (b-1) an organoaluminum oxy compound,
In the presence of an olefin polymerization catalyst comprising (b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and (b-3) at least one compound selected from organoaluminum compounds And at least one olefin selected from olefins having 2 or more carbon atoms, and a method for producing an olefin polymer:

[In Formula [1],
R ¹ to R ⁴ each independently represents a group selected from a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group and a silicon-containing group, and two adjacent groups are bonded to form a ring. May be;
R ⁵ to R ⁹ each independently represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group and a silicon-containing group, and two adjacent groups are They may combine to form a ring;
R ¹⁰ to R ¹² each independently represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group and a silicon-containing group;
Y represents a carbon atom or a silicon atom;
M represents Ti, Zr or Hf;
Q is a structure selected from a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair; j Represents an integer of 1 to 4, and when j is 2 or more, a plurality of Qs may be the same or different from each other. ]
In [2] the general formula [1] is a group selected from a halogen-containing hydrocarbon group of R ¹ and R ⁴ are hydrocarbon groups and having 1 to 40 carbon atoms each independently having a carbon number of 1 to a 40, R ² And at least one group of R ³ is a group selected from a hydrocarbon group having 1 to 40 carbon atoms and a silicon-containing group.
[3] In the general formula [1], R ¹ and R ⁴ are each independently a group selected from an aryl group having 6 to 20 carbon atoms and a halogen-containing aryl group having 6 to 20 carbon atoms. The method for producing an olefin polymer according to the above [1] or [2].
[4] In the general formula [1], R ¹² is a group selected from a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, and a halogen-containing hydrocarbon group having 1 to 40 carbon atoms. [1] The process for producing an olefin polymer according to any one of [3].
[5] In the general formula [1], R ¹⁰ to R ¹¹ are all hydrogen atoms, R ¹² is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms. The olefin polymer according to any one of the above [1] to [4], wherein the olefin polymer is a group selected from halogen-containing aryl groups, or R ¹⁰ to R ¹² are all hydrogen atoms Manufacturing method.
[6] In the general formula [1], R ⁵ to R ⁹ are each independently a group selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms. [5] The method for producing an olefin polymer according to any one of [5].
[7] The method for producing an olefin polymer according to any one of [1] to [6], wherein the olefin polymerization catalyst further contains a carrier (C).
[8] The method for producing an olefin polymer according to any one of [1] to [7], wherein at least a part of the olefin is propylene.
[9] Any of the above [1] to [8], wherein the bridged metallocene compound represented by the general formula [1] has a solubility in n-hexane at 25 ° C. of 0.5 mmol / L or more. A method for producing the olefin polymer according to claim 1.
[10] The above [1] to [9], wherein a solution having a concentration of the bridged metallocene compound represented by the general formula [1] of 0.05 mmol / L to 1.0 mol / L is supplied to the polymerization system. ] The manufacturing method of the olefin polymer as described in any one of.
[11] The method for producing an olefin polymer according to any one of [1] to [10], wherein the polymerization temperature is 50 to 150 ° C.
[12] Melting point (Tm) measured with a differential scanning calorimeter of the resulting propylene polymer when the polymerization temperature is 50 to 150 ° C. (if multiple crystal melting peaks are observed, the melting point based on the high temperature side peak) (Tm)) is 145 to 170 ° C., the intrinsic viscosity ([η]) measured in decalin at 135 ° C. is 1.25 dl / g or more, and the weight average molecular weight measured by gel permeation chromatography ( Mw) is 97,000 or more, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1 to 3, [1] to [11] The manufacturing method of the propylene polymer as described in any one of these.

According to the present invention, when an olefin polymer such as propylene is polymerized to produce an olefin polymer having a high melting point and a high molecular weight, it is possible to provide a production method that is advantageous in an industrial production method and has high productivity. it can.

The method for producing an olefin polymer according to the present invention comprises an olefin having 2 or more carbon atoms (preferably α) in the presence of an olefin polymerization catalyst comprising (A) a bridged metallocene compound described later and (B) a compound described later. At least one olefin selected from olefins).

Hereinafter, the invention relates to a catalyst for olefin polymerization comprising a crosslinked metallocene compound (A) and a compound (B) used in the present invention, and a method for polymerizing an olefin having 2 or more carbon atoms in the presence of the olefin polymerization catalyst. The best mode for carrying out will be described sequentially.

[Olefin polymerization catalyst]
The catalyst for olefin polymerization used in the present invention reacts with the bridged metallocene compound (A), (B) (b-1) an organoaluminum oxy compound, and (b-2) the bridged metallocene compound (A) to produce an ion pair. And (b-3) at least one compound selected from organoaluminum compounds as essential components. Further, the carrier (C) and the organic compound component (D) may be included as optional components.

<< Bridged metallocene compound (A) >>
The bridged metallocene compound (A) used in the present invention is represented by the following general formula [1].

In the formula [1], the meaning of each symbol is as follows.

R ¹ to R ⁴ are each independently a group selected from a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group and a silicon-containing group. Further, two groups (for example, R ¹ and R ² , R ³ and R ⁴ ) bonded to adjacent ring carbons out of R ¹ to R ⁴ may be bonded to form a ring.

R ⁵ to R ⁹ are each independently a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group, and a silicon-containing group. In addition, two groups (eg, R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ ) bonded to adjacent ring carbons among R ⁵ to R ⁹ are bonded. May form a ring.

R ¹⁰ to R ¹² are each independently a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group, and a silicon-containing group.

Y represents a carbon atom or a silicon atom.

M represents Ti, Zr or Hf.

Q is a structure selected from a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair. j represents an integer of 1 to 4, and when j is 2 or more, a plurality of Qs may be the same or different from each other.

Hereinafter, groups constituting the bridged metallocene compound (A) will be described.

In this specification, the term “group” is used to include atoms.

About -R ¹ ~ R ¹² -
The hydrocarbon group listed as R ¹ to R ¹² is preferably a hydrocarbon group having 1 to 40 carbon atoms, and more preferably a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a saturated alicyclic group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. A linear alkyl group such as n-decanyl group; iso-propyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1 Illustrative branched alkyl groups such as -methyl-1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl Is done.

Examples of the saturated alicyclic group having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; and alicyclic polycyclic groups such as norbornyl group and adamantyl group. .

Examples of the aryl group having 6 to 20 carbon atoms include an aryl group in which all groups bonded to an aromatic carbon such as a phenyl group, a naphthyl group, a phenanthryl group, an anthracenyl group, and a biphenyl group are hydrogen atoms (hereinafter referred to as “unsubstituted aryl group”). O-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, n-propylphenyl group, iso-propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert- Examples thereof include alkylaryl groups such as butylphenyl group and xylyl group.

As the aralkyl group having 7 to 20 carbon atoms, all the groups bonded to aromatic carbon such as benzyl group, cumyl group, α-phenethyl group, β-phenethyl group, diphenylmethyl group, naphthylmethyl group, neophyll group, etc. are hydrogen atoms. An aralkyl group (hereinafter also referred to as “unsubstituted aralkyl group”); o-methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group, ethylbenzyl group, n-propylbenzyl group, iso-propylbenzyl group And alkylaralkyl groups such as n-butylbenzyl group, sec-butylbenzyl group and tert-butylbenzyl group.

The hydrocarbon group is particularly preferably a hydrocarbon group having 1 to 10 carbon atoms.

Examples of the halogen-containing hydrocarbon group listed as R ¹ to R ¹² include groups in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom. Specifically,
Halogen-containing alkyl groups such as fluoroalkyl groups such as trifluoromethyl groups;
Fluoroaryl groups such as pentafluorophenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, chloroaryl group such as chloronaphthyl group, o-bromophenyl group, m-bromophenyl group, p-bromophenyl A part of or all of the above-mentioned unsubstituted aryl groups such as iodoaryl groups such as bromoaryl groups such as bromonaphthyl groups, o-iodophenyl groups, m-iodophenyl groups, p-iodophenyl groups and iodonaphthyl groups A group in which a hydrogen atom is substituted with a halogen atom; a fluoroalkylaryl group such as a trifluoromethylphenyl group, a bromoalkylaryl group such as a bromomethylphenyl group or a dibromomethylphenyl group, an iodomethylphenyl group, or a diiodomethylphenyl group The iodoalkyl aryl Halogen-containing aryl group such as; the part of the hydrogen atoms of the alkyl aryl group group substituted with a halogen atom such as;
chloroaralkyl groups such as o-chlorobenzyl group, m-chlorobenzyl group, p-chlorobenzyl group, chlorophenethyl group, o-bromobenzyl group, m-bromobenzyl group, p-bromobenzyl group, bromophenethyl group, etc. A part of the hydrogen atoms of the unsubstituted aralkyl group such as a bromoaralkyl group, an o-iodobenzyl group, an m-iodobenzyl group, a p-iodobenzyl group, an iodophenethyl group, or the like is substituted with a halogen atom. Illustrative are halogen-containing aralkyl groups such as groups.

Examples of nitrogen-containing groups listed as R ¹ to R ¹² include a nitro group, a cyano group, an N-methylamino group, an N, N-dimethylamino group, and an N-phenylamino group.

Examples of the oxygen-containing group listed as R ¹ to R ¹² include a methoxy group, an ethoxy group, and a phenoxy group.

Examples of silicon-containing groups listed as R ¹ to R ¹² include alkylsilyl groups such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group; Examples include arylsilyl groups such as silyl group, diphenylmethylsilyl group, and triphenylsilyl group.

Examples of the halogen atom listed as R ⁵ to R ¹² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Further, at least one set of two adjacent groups selected from R ¹ to R ⁴ and R ⁵ to R ⁹ may be bonded to form a ring. Examples of the ring structure include 1-methyl-2-naphthalenyl group, 3-methyl-2-naphthalenyl group, 1-methyl-2- (5,6,7,8-tetrahydro) naphthalenyl group, 3-methyl-2- (5,6,7,8-tetrahydro) naphthalenyl group, 7-methyl-1H-6-indenyl group, 6-methyl-1H-5-indenyl group, 7-methyl-6-benzofuranyl group, 6-methyl-5 -Benzofuranyl group, 7-methyl-6-benzothiophenyl group, 6-methyl-5-benzothiophenyl group.

R ¹ and R ⁴ are preferably each independently the above hydrocarbon group or halogen-containing hydrocarbon group, more preferably the above aryl group or halogen-containing aryl group, a phenyl group, an alkylphenyl group, or these It is more preferable that a part of the hydrogen atoms in the group is a group substituted with a halogen atom. R ¹ and R ⁴ are preferably the same group.

One or more groups of R ² and R ³ are preferably groups selected from the hydrocarbon group and the silicon-containing group. Further, R ² and R ³ are preferably each independently the hydrocarbon group or silicon-containing group, more preferably the hydrocarbon group, and particularly preferably the alkyl group. R ² and R ³ are preferably the same group.

R ⁵ to R ⁹ are each independently preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms, and R ⁵ to R ⁹ are all hydrogen atoms, R ⁵ , R ⁶ , R ⁸ R ⁹ is more preferably a hydrogen atom, and R ⁷ is more preferably a halogen atom or an alkyl group having 1 to 20 carbon atoms.

R ¹⁰ to R ¹¹ are each preferably a hydrogen atom; R ¹² is preferably a hydrogen atom, the above hydrocarbon group or a halogen-containing hydrocarbon group, and the above alkyl group, aryl group or halogen-containing aryl. It is more preferably a group, more preferably an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkylphenyl group, or a group in which a part of these groups is substituted with a halogen. It is presumed that an olefin polymer having a high melting point and a high molecular weight is produced by the electronic or steric effects of R ¹⁰ to R ¹² or both.

By using the bridged metallocene compound (A) having the above substituent, an olefin polymer having a high melting point can be obtained. This is because the bridged metallocene compound (A) catalyzes the production of a highly stereoregular olefin polymer. For this reason, even an olefin polymer synthesized at a temperature higher than room temperature, preferably a temperature much higher than room temperature, can exhibit good moldability, increase the value of the product and industrially produce olefin polymers. The cost performance when doing so is improved.

Further, by using the bridged metallocene compound (A) having the above substituent, an olefin polymer having a large molecular weight can be obtained. This is because the bridged metallocene compound (A) catalyzes the production of a high molecular weight olefin polymer. For this reason, it becomes possible to synthesize an olefin polymer at a temperature not lower than room temperature, preferably a temperature significantly higher than room temperature, and the cost performance when industrially producing the olefin polymer is improved.

Furthermore, the bridged metallocene compound (A) has excellent solubility in hydrocarbon solvents. Specifically, the bridged metallocene compound (A) has a solubility in a hydrocarbon solvent having 4 to 10 carbon atoms (25 ° C.), preferably 0.5 mmol / L or more. More preferably, it is 0.7 mmol / L or more, More preferably, it is 0.9 mmol / L or more. More specifically, the solubility of the bridged metallocene compound (A) is preferably 0.5 mmol / L or more, more preferably 0.7 mmol / L or more, and still more preferably 0 with respect to n-hexane at 25 ° C. .9 mmol / L or more. In general, the upper limit is preferably 10 mol / L or less, more preferably 1 mol / L or less.

The bridged metallocene compound in which the ligand has a crosslinked structure generally has a rigid structure and is relatively strongly crystallized, and the solubility in hydrocarbon solvents tends to decrease. However, the bridged metallocene compound (A) used in the present invention has an asymmetric structure in which the structure of the bridge portion, specifically, the structure of the two substituents bonded to Y in formula (1) are different. It is presumed that the degree of crystallization is loose and the solubility in hydrocarbon solvents tends to be high.

For example, Non-Patent Document 1 discloses that metallocene compounds generally tend to have extremely high olefin polymerization activity. Such highly active compounds generally tend to be susceptible to the effects of impurities, specifically poisoning and deactivation. However, the bridged metallocene compound (A) used in the present invention is excellent in solubility in a hydrocarbon solvent as described above, whereby a catalyst solution can be prepared using a smaller amount of solvent. As a result, the effects of poisoning and deactivation due to impurities that may be slightly contained in the solvent used are suppressed, and an improvement in the productivity of the olefin polymer can be expected. Such an effect is a useful performance that is expected to reduce the possibility of being affected by the lot of the solvent to be used, especially when the production of an olefin polymer is commercialized.

-About Y, M, Q and j-
Y represents a carbon atom or a silicon atom, preferably a carbon atom.

M represents Ti, Zr or Hf, preferably Zr or Hf, particularly preferably Zr. By using the cross-linked metallocene compound (A) having the central metal and the cross-linking part, a high molecular weight and high melting point olefin polymer can be efficiently produced.

Q is a structure selected from a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair.

Examples of the halogen atom listed as Q include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As the hydrocarbon group listed as Q, an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms are preferable. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, iso-propyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, , 1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1, Examples include a 1,3-trimethylbutyl group and a neopentyl group; examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclohexylmethyl group, a cyclohexyl group, and a 1-methyl-1-cyclohexyl group. More preferably, the hydrocarbon group has 5 or less carbon atoms.

Neutral conjugated or non-conjugated dienes having 10 or less carbon atoms include s-cis- or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4- Diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1, 3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s- cis - or s- trans eta ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

Examples of the anion ligand include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate.

Neutral ligands that can be coordinated by lone pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran (THF), diethyl ether, dioxane, 1,2-dimethoxy Examples are ethers such as ethane.

Q is preferably a halogen atom or an alkyl group having 1 to 5 carbon atoms.

J is an integer of 1 to 4, preferably 2.

One preferred form of the bridged metallocene compound (A) is represented by the following general formula [2].

In the formula [2], R ¹ to R ⁴ , R ⁷ , R ¹² , Y, M, Q and j are defined as R ¹ to R ⁴ , R ⁷ , R ¹² , Y, M in the above formula [1]. , Q and j are identical. Preferably, R ¹ and R ⁴ are an aryl group having 6 to 20 carbon atoms or a halogen-containing aryl group having 6 to 20 carbon atoms, R ² and R ³ are alkyl groups having 1 to 10 carbon atoms, and R ⁷ Is a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, and R ¹² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.

<Examples of bridged metallocene compounds>
Specific examples of the bridged metallocene compound (A) represented by the general formula [1] are shown below, but the scope of the present invention is not particularly limited thereby. In the present invention, the crosslinked metallocene compound (A) may be used alone or in combination of two or more.

For convenience, the ligand structure excluding MQ _j (metal part) of the metallocene compound is divided into three parts: Bridge (bridge part), Flu (fluorenyl part) and Cp (cyclopentadienyl part). The structure of the crosslinked portion is divided into three in terms of notation. Abbreviations of each group of the crosslinked portion are shown in Table 1, and specific examples of the structure of the crosslinked portion are shown in Tables 2 to 3. α represents —CR ¹⁰ R ¹¹ R ¹² , β represents —PhR ⁵ R ⁶ R ⁷ R ⁸ R ⁹ , and γ represents Y.

According to the above table, No. B-24 means a combination of α1-β2-γ1, and the structure of the bridge (crosslinked portion) is represented by the following formula.

Next, specific examples of the structure of the fluorenyl moiety are shown in Table 4.

The combinations of the bridging moiety and the fluorenyl moiety of the metallocene compound are shown in the following table.

According to the above table, no. The ligand structure of 944 means a combination of B-24 and δ5. When MQ _{j of} the metal moiety is ZrCl ₂ , the following metallocene compound is exemplified.

Specific examples of MQ _j include ZrCl ₂ , ZrBr ₂ , ZrMe ₂ , Zr (OTs) ₂ , Zr (OMs) ₂ , Zr (OTf) ₂ , TiCl ₂ , TiBr ₂ , TiMe ₂ , Ti (OTs). _{2, Ti (OMs) 2,} Ti (OTf) 2, HfCl 2, HfBr 2, HfMe 2, Hf (OTs) 2, Hf (OMs) 2, etc. Hf (OTf) ₂ and the like. Ts represents a p-toluenesulfonyl group, Ms represents a methanesulfonyl group, and Tf represents a trifluoromethanesulfonyl group.

The bridged metallocene compound (A) represented by the general formula [1] used in the present invention can be produced by a known method, and the production method is not particularly limited. Examples of known production methods include those described in the pamphlet of WO 2001/027124 and WO 2004/087775 by the applicant.

<< Compound (B) >>
In the present invention, the compound (B) is used as a component of the olefin polymerization catalyst. Compound (B) is selected from (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with a bridged metallocene compound (A) to form an ion pair, and (b-3) an organoaluminum compound. At least one kind. Of these, the organoaluminum oxy compound (b-1) is preferred.

<Organic aluminum oxy compound (b-1)>
Examples of the organoaluminum oxy compound (b-1) include conventionally known aluminoxanes such as a compound represented by the following general formula [3] and a compound represented by the following general formula [4], and a compound represented by the following general formula [5]. Examples thereof include a modified methylaluminoxane having a structure represented by the following formula, and a boron-containing organoaluminum oxy compound represented by the following general formula [6].

In the formulas [3] and [4], R represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group, and n represents an integer of 2 or more, preferably 3 or more, more preferably 10 or more. In the present invention, methylaluminoxane in which R is a methyl group in formulas [3] and [4] is preferably used.

In the formula [5], R represents a hydrocarbon group having 2 to 10 carbon atoms, and m and n each independently represents an integer of 2 or more. A plurality of R may be the same or different from each other.

The modified methylaluminoxane [5] can be prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such modified methylaluminoxane [5] is generally called MMAO (modified （methyl aluminoxane). MMAO can be prepared specifically by the methods listed in US4960878 and US5041584.

In addition, modified methylaluminoxane prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem Co., Ltd. (namely, R in the above general formula [5] is an isobutyl group) is named MMAO or TMAO. Is produced commercially.

MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, unlike a compound that is insoluble or hardly soluble in benzene such as a compound represented by the above general formula [3] or [4], MMAO is an aliphatic hydrocarbon, alicyclic carbonization. It is soluble in hydrogen and aromatic hydrocarbons.

In the formula [6], R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. A plurality of R ^{d 's} each independently represents a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 10 carbon atoms.

In the present invention, an olefin polymer can be produced even at a high temperature as described later. Therefore, one of the features of the present invention is that a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can also be used. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like are also included. It can be used suitably.

The “benzene-insoluble” organoaluminum oxy compound means that the amount of the compound dissolved in benzene at 60 ° C. is usually 10% by weight or less, preferably 5% by weight or less, particularly preferably in terms of Al atom. An organoaluminum oxy compound that is 2% by weight or less and is insoluble or hardly soluble in benzene.

In the present invention, the organoaluminum oxy compound (b-1) exemplified above may be used alone or in combination of two or more.

<Compound (b-2) which forms an ion pair by reacting with the bridged metallocene compound (A)>
As the compound (b-2) that reacts with the bridged metallocene compound (A) to form an ion pair (hereinafter sometimes abbreviated as “ionic compound (b-2)”), JP-A-1-501950 is disclosed. JP, 1-502036, JP 3-179005, JP 3-179006, JP 3-207703, JP 3-207704, JP 2004-51676. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in U.S. Pat. No. 5,321,106. Furthermore, heteropoly compounds and isopoly compounds are also exemplified. Of these, the ionic compound (b-2) is preferably a compound represented by the following general formula [7].

In the formula [7], R ^{e +} is exemplified by H ⁺ , oxonium cation, carbenium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^f , R ^g , R ^h and R ⁱ each independently represents an organic group, preferably a group selected from an aryl group and a halogen-containing aryl group.

Examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

Examples of the ammonium cation include trialkylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation; N, N, N-dialkylanilinium cations such as N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N, 2,4,6-pentamethylanilinium cation; diisopropylammonium cation, dicyclohexylammonium cation, etc. Of the dialkylammonium cation.

Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

As R ^{e +} , among the above examples, a carbenium cation and an ammonium cation are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

1. When R ^{e +} is a carbenium cation (carbenium salt)
Examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methylphenyl) carbene. Examples thereof include nium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

2. When R ^{e +} is an ammonium cation (ammonium salt)
Examples of ammonium salts include trialkylammonium salts, N, N-dialkylanilinium salts, and dialkylammonium salts.

Specific examples of the trialkylammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis ( o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4 -Dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate Tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis ( o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, Dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate DOO, dioctadecyl methyl ammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecyl methyl ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate.

Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and N, N-dimethylaniliniumtetrakis. (3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5 -Ditrifluoromethylphenyl) borate, N, N, 2,4,6-pentamethylanilinium tetraphenylborate, N, N, 2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate The

Specific examples of the dialkylammonium salt include diisopropylammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

The ionic compound (b-2) may be used alone or in combination of two or more.

<Organic aluminum compound (b-3)>
Examples of the organoaluminum compound (b-3) include an organoaluminum compound represented by the following general formula [8], and a complex alkylated product of a group 1 metal of the periodic table represented by the following general formula [9] and aluminum. Illustrated.

R ^a _m Al (OR ^b ) _n H _p X _q [8]
In the formula [8], R ^a and R ^b each independently represent a group selected from a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3.

M ² AlR ^a ₄ ... [9]
In the formula [9], M ² represents Li, Na or K, and a plurality of R ^a each independently represents a group selected from a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

Examples of the organoaluminum compound [8] include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, and trioctylaluminum;
Tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tritolylaluminum;
Dialkylaluminum hydrides such as diisopropylaluminum hydride, diisobutylaluminum hydride;
Formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y and z are each a positive number, and z ≦ 2x.) Isoprenyl represented by like Alkenyl aluminum such as aluminum;
Alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide ;
(Wherein, R ^a and R ^b are. Synonymous with R ^a and R ^b in the formula [8]) formula R ^a _2.5 Al (OR ^b) _0.5 partially alkoxy having an average composition represented by Alkyl aluminum; alkyl aluminum aryloxides such as diethyl aluminum phenoxide and diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide); dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum Dialkylaluminum halides such as bromide and diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride Illustrative are partially partially alkylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycyclyl, ethylaluminum ethoxybromide.

Examples of the complex alkylated product [9] include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . A compound similar to the complex alkylated product [9] can also be used, and an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom is exemplified. An example of such a compound is (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

As the organoaluminum compound (b-3), trimethylaluminum and triisobutylaluminum are preferable because they are easily available. The organoaluminum compound (b-3) may be used alone or in combination of two or more.

<< Carrier (C) >>
In the present invention, the carrier (C) may be used as a component of the olefin polymerization catalyst. The carrier (C) is an inorganic compound or an organic compound, and is a granular or particulate solid.

<Inorganic compounds>
Examples of the inorganic compound include porous oxides, inorganic halides, clay minerals, clay (usually composed of the clay mineral as a main component), ion-exchangeable layered compounds (most clay minerals are ion-exchangeable). A layered compound)).

Examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ ; a composite or mixture containing these oxides. The Examples of the composite or mixture include natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO _2. -TiO ₂ -MgO is exemplified. Among these, porous oxides containing as a main component one or both of SiO ₂ and Al ₂ O ₃ are preferable.

The porous oxide has different properties depending on the type and production method, but the particle size is preferably 10 to 300 μm, more preferably 20 to 200 μm; the specific surface area is preferably 50 to 1000 m ² / g, Preferably it is in the range of 100 to 700 m ² / g; the pore volume is preferably in the range of 0.3 to 3.0 cm ³ / g. Such a porous oxide is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Examples of the inorganic halide include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. In addition, it is possible to use a component that is dissolved in a fine particle by a precipitating agent after the inorganic halide is dissolved in a solvent such as alcohol.

The above-mentioned clay, clay mineral, and ion-exchange layered compound are not limited to natural products, and artificial synthetic products can also be used. In addition, the said ion exchange layered compound is a compound which has the crystal structure where the surface comprised by an ionic bond etc. was piled up in parallel with weak mutual bond force, and is a compound which can contain the ion contained.

Specifically, the clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, synthetic mica, etc. And kaolinite, nacrite, dickite, hectorite, teniolite and halloysite; examples of the ion-exchangeable layered compound have a layered crystal structure such as hexagonal close-packed packing type, antimony type, CdCl ₂ type, CdI ₂ type Examples are ionic crystalline compounds. Specifically, examples of the ion-exchange layered compound include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α- Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ Examples thereof include crystalline acidic salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.

Further, the ion-exchangeable layered compound may be a layered compound in which the interlayer is expanded by exchanging the exchangeable ions between the layers with another large bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. For example, an oxide column (pillar) can be formed between layers by intercalating the following metal hydroxide ions between layers of the layered compound and then heat-dehydrating. The introduction of another substance between the layers of the layered compound is called intercalation.

Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ ; metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group); metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Is exemplified. These guest compounds may be used alone or in combination of two or more.

In addition, when the guest compound is intercalated, a metal alkoxide (R is a hydrocarbon group, etc.) such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ is hydrolyzed and polycondensed. The obtained polymer, a colloidal inorganic compound such as SiO _2, etc. can also coexist.

Among the inorganic compounds, clay minerals and clays are preferable, and montmorillonite group, vermiculite, hectorite, teniolite and synthetic mica are particularly preferable.

<Organic compounds>
Examples of the organic compound include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer synthesized mainly from an olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene; Examples of synthesized (co) polymers; modified products of these (co) polymers.

<< Organic compound component (D) >>
In the present invention, the organic compound component (D) may be used as a component of the olefin polymerization catalyst. The organic compound component (D) is used for the purpose of improving the polymerization performance in the olefin polymerization reaction and the physical properties of the olefin polymer, if necessary. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

<< Configuration and Preparation of Olefin Polymerization Catalyst >>
The components of the olefin polymerization catalyst are preferably used in the following ratios.

<1> When olefin polymerization is performed using the above olefin polymerization catalyst, the crosslinked metallocene compound (A) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 1 liter per reaction volume. It is used in such an amount that it becomes 10 ⁻² mol.

<2> When the organoaluminum oxy compound (b-1) is used as a component of the olefin polymerization catalyst, the compound (b-1) is crosslinked with the aluminum atom (Al) in the compound (b-1). The metallocene compound (A) is used in such an amount that the molar ratio [Al / M] to all transition metal atoms (M) in the metallocene compound (A) is usually 0.01 to 5000, preferably 0.05 to 2000.

<3> When the ionic compound (b-2) is used as a component of the catalyst for olefin polymerization, the compound (b-2) is a combination of the compound (b-2) and the bridged metallocene compound (A). The molar ratio [(b-2) / M] with the transition metal atom (M) is usually 1 to 10, preferably 1 to 5.

<4> When the organoaluminum compound (b-3) is used as a component of the olefin polymerization catalyst, the compound (b-3) is added to the compound (b-3) and the bridged metallocene compound (A). The molar ratio [(b-3) / M] with the transition metal atom (M) is usually 10 to 5000, preferably 20 to 2000.

<5> When the organic compound component (D) is used as a component of the olefin polymerization catalyst, when the compound (B) is an organoaluminum oxy compound (b-1), the organic compound component (D) and the compound In an amount such that the molar ratio [(D) / (b-1)] to (b-1) is usually 0.01 to 10, preferably 0.1 to 5; compound (B) is an ion When the organic compound (b-2) is used, the molar ratio [(D) / (b-2)] of the organic compound component (D) and the compound (b-2) is usually 0.01 to 10 Preferably in an amount of 0.1 to 5; when the compound (B) is an organoaluminum compound (b-3), the moles of the organic compound component (D) and the compound (b-3) The amount [(D) / (b-3)] is usually 0.005 to 2, preferably 0.01 to 1. It is.

The catalyst for olefin polymerization used in the present invention can be used by dissolving the bridged metallocene compound (A) and compound (B), which are catalyst components, in a solvent. That is, in the present invention, the olefin polymerization catalyst can be supplied to the polymerization system as a catalyst solution.

As the solvent, generally a hydrocarbon solvent having 4 to 10 carbon atoms can be used. In the present invention, as described above, a high concentration catalyst solution (solvent: hydrocarbon solvent) of the bridged metallocene compound (A) can be prepared. From the viewpoint of polymerization activity, it is preferable to supply a catalyst solution having a bridged metallocene compound (A) concentration of 0.03 mmol / L to 2.0 mol / L to the polymerization system, more preferably 0.04 mmol / L to 1.. 5 mol / L, more preferably 0.05 mmol / L to 1.0 mol / L.

Examples of the hydrocarbon solvent having 4 to 10 carbon atoms that can be used for preparing the catalyst solution include hydrocarbon solvents having 4 carbon atoms such as butane, isobutane, cyclobutane, and methylcyclopropane;
Hydrocarbon solvents having 5 carbon atoms such as pentane, isopentane, neopentane, cyclopentane, methylcyclobutane, 1,1-dimethylcyclopropane, 1,2-dimethylcyclopropane, ethylcyclopropane;
Hexane, 3-methylpentane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, methylcyclopentane, 1,1-dimethylcyclobutane, 1,2-dimethylcyclobutane, 1,3- C6 hydrocarbon solvents such as dimethylcyclobutane, ethylcyclobutane, 1,1,2-trimethylcyclopropane, 1-ethyl-1-methylcyclopropane, propylcyclopropane, isopropylcyclopropane;
Heptane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,2,3 -Trimethylbutane, methylcyclohexane, 1,2-dimethylpentane, 1,3-dimethylpentane, 1,2,3-trimethylbutane, cycloheptane, methylcyclohexane, 1,1-dimethylcyclopentane, 1,2-dimethylcyclo Pentane, 1,3-dimethylcyclopentane, ethylcyclopentane, propylcyclobutane, 1,1,2,2-tetramethylcyclopropane, 1,1,2,3-tetramethylcyclopropane, 1,1-diethylcyclopropane 1-isopropyl-1-methylcyclopropane, 1-isopropyl 2-methyl-cyclopropane, 1-propyl-2-methyl cyclopropane, hydrocarbon solvents having a carbon number of 7 or butyl cyclopropane;
Octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethyl Hexane, 3,4-dimethylhexane, 3-ethylhexane, 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, 2-methyl-3-ethylpentane, cyclooctane, methylcycloheptane, 1,1-dimethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, ethylcyclohexane, 1,1 , 2-Trimethylcyclopentane, 1,1,3-trimethylcyclopenta 1,2,3-trimethylcyclopentane, 1,2,4-trimethylcyclopentane, 1-ethyl-1-methylcyclopentane, 1-ethyl-2-methylcyclopentane, 1-ethyl-3-methylcyclopentane , Propylcyclopentane, isopropylcyclopentane, 1,2,3,4-tetramethylcyclobutane, 1,1,3,3-tetramethylcyclobutane, 2,2,3,3-tetramethylcyclobutane, 1,2-diethyl Hydrocarbon solvents having 8 carbon atoms such as cyclobutane, 1-butyl-2-methylcyclopropane, pentylcyclopropane, isopentylcyclopropane;
Nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,2-dimethylheptane, 2,3-dimethylheptane, 2,4-dimethylheptane, 2,5-dimethylheptane, 2,6-dimethyl Heptane, 4,4-dimethylheptane, 2-ethylheptane, 3-ethylheptane, 4-ethylheptane, 2,2,3-trimethylhexane, 2,2,4-trimethylhexane, 2,2,5-trimethylhexane 2,3,3-trimethylhexane, 2,3,4-trimethylhexane, 2,3,5-trimethylhexane, 2,4,4-trimethylhexane, 3,3,4-trimethylhexane, 3-ethyl- 2-methylhexane, 3-ethyl-3-methylhexane, 4-ethyl-2-methylhexane, 4-ethyl-3-methylhexane 2,2,3,3-tetramethylpentane, 2,2,3,4-tetramethylpentane, 2,2,4,4-tetramethylpentane, 2,3,3,4-tetramethylpentane, 2, 2-dimethyl-3-ethylpentane, 2,2-diethylpentane, 2,3-diethylpentane, cyclononane, methylcyclooctane, ethylcycloheptane, 1,1-dimethylcycloheptane, 1,2-dimethylcycloheptane, 1 , 3-dimethylcycloheptane, 1,4-dimethylcycloheptane, propylcyclohexane, isopropylcyclohexane, 1-ethyl-2-methylcyclohexane, 1-ethyl-3-methylcyclohexane, 1-ethyl-4-methylcyclohexane, 1, 1,2-trimethylcyclohexane, 1,1,3-trimethylcyclohex 1,1,4-trimethylcyclohexane, 1,2,3-trimethylcyclohexane, 1,2,4-trimethylcyclohexane, butylcyclopentane, isobutylcyclopentane, 2-cyclopentylbutane, 1,2-diethylcyclopentane, 1-isopropyl-3-methylcyclopentane, 1-methyl-2-propylcyclopentane, 2-ethyl-1,1-dimethylcyclopentane, 1,1,3,3-tetramethylcyclopentane, 1,1,3 , 4-tetramethylcyclopentane, 1,2,3,4-tetramethylcyclopentane, 1,1,2,3,3-pentamethylcyclobutane, 1,2-dipropylcyclopropane, 1-hexylcyclopropane, 1-pentyl-1-methylcyclopropane, 1-pentyl-2-methylcyclopro C9 hydrocarbon solvent such as bread;
Decane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2,2-dimethyloctane, 2,3-dimethyloctane, 2,4-dimethyloctane, 2,5-dimethyloctane, 2,6- Dimethyloctane, 2,7-dimethyloctane, 3,3-dimethyloctane, 3,4-dimethyloctane, 3,5-dimethyloctane, 3,6-dimethyloctane, 4,4-dimethyloctane, 4,5-dimethyl Octane, 3-ethyloctane, 4-ethyloctane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethylheptane, 2,2,5-trimethylheptane, 2, 2,6-trimethylheptane, 2,3,3-trimethylheptane, 2,3,4-trimethylheptane, 2,3,5 Trimethylheptane, 2,3,6-trimethylheptane, 2,4,4-trimethylheptane, 2,4,5-trimethylheptane, 2,4,6-trimethylheptane, 2,5,5-trimethylheptane, 2- Methyl-3-ethylheptane, 2-methyl-4-ethylheptane, 3-ethyl-3-methylheptane, 3-ethyl-4-methylheptane, 3-ethyl-5-methylheptane, 3-methyl-4-ethyl Heptane, 5-ethyl-2-methylheptane, 3,3,4-trimethylheptane, 3,3,5-trimethylheptane, 3,4,4-trimethylheptane, 3,4,5-trimethylheptane, 4-propyl Heptane, 4-isopropylheptane, 2,2,3,3-tetramethylhexane, 2,2,3,4-tetramethylhexane, 2,2,3,5 Tetramethylhexane, 2,2,4,4-tetramethylhexane, 2,2,4,5-tetramethylhexane, 2,2,5,5-tetramethylhexane, 2,3,3,4-tetramethyl Hexane, 2,3,3,5-tetramethylhexane, 2,3,4,4-tetramethylhexane, 2,3,4,5-tetramethylhexane, 3,3,4,4-tetramethylhexane, 2,2-dimethyl-3-ethylhexane, 2,3-dimethyl-3-ethylhexane, 2,3-dimethyl-4-ethylhexane, 2,4-dimethyl-4-ethylhexane, 2,5-dimethyl- 3-ethylhexane, 3,3-dimethyl-4-ethylhexane, 3,4-dimethyl-3-ethylhexane, 3-ethyl-2,4-dimethylhexane, 4-ethyl-2,2-dimethylhexa 3,3-diethylhexane, 3,4-diethylhexane, 2,2,3,4,4-pentamethylpentane, 2,2,3,4,4-pentamethylpentane, 2,2,3-trimethyl -3-Ethylpentane, 2,2,4-trimethyl-3-ethylpentane, 2,3,4-trimethyl-3-ethylpentane, 2,4-dimethyl-3-isopropylpentane, 2-methyl-3-3 -Diethylpentane, 4-ethyl-4-methylpentane, cyclodecane, methylcyclononane, 1,5-dimethylcyclooctane, ethylcyclooctane, cycloheptane, 1,1,2,3-tetramethylcyclohexane, 1,1, 3,3-tetramethylcyclohexane, 1,1,3,5-tetramethylcyclohexane, 1,1,4,4-tetramethylcyclohexane, , 2,2,4-tetramethylcyclohexane, 1,2,3,4-tetramethylcyclohexane, 1,2,3,5-tetramethylcyclohexane, 1,2,4,5-tetramethylcyclohexane, butylcyclohexane, 1,3-diethylcyclohexane, 1,4-diethylcyclohexane, 1-ethyl-2-propylcyclohexane, 1,3-dimethyl-5-ethylcyclohexane, 1-ethyl-2,3-dimethylcyclohexane, 1-ethyl-2 , 4-Dimethylcyclohexane, 1-isopropyl-1-methylcyclohexane, 1-isopropyl-2-methylcyclohexane, 1-isopropyl-3-methylcyclohexane, 1-isopropyl-4-methylcyclohexane, 1-methyl-2-propylcyclohexane , 1-methyl-3-propyl Pyrcyclohexane, 2-ethyl-1,3-dimethylcyclohexane, sec-butylcyclohexane, tert-butylcyclohexane, isobutylcyclohexane, 1,2,3,4,5-pentamethylcyclopentane, 1,2,3-trimethyl- 4-ethylcyclopentane, 1,2-dimethyl-3-isopropylcyclopentane, 1-ethyl-3-isopropylcyclopentane, 1-methyl-2,4-diethylcyclopentane, 1-methyl-2-butylcyclopentane, 1-methyl-3-tert-butylcyclopentane, 1-methyl-3-isobutylcyclopentane, 2-isopropyl-1,3-dimethylcyclopentane, 2-cyclopentylpentane, 2-methylbutylcyclopentane, isopentylcyclopentane , Pencil Lopentane, 2-ethyl-1-methyl-3-propylcyclobutane, 1,1,2-trimethyl-3-isobutylcyclopropane, 1,1-dimethyl-2-pentylcyclopropane, 1,2-dimethyl-1-pentyl Cyclopropane, 1,2-dimethyl-3-pentylcyclopropane, 1-ethyl-2-pentylcyclopropane, 1-hexyl-2-methylcyclopropane, 1-methyl-2- (1-methylpentyl) cyclopropane, A hydrocarbon solvent having 10 carbon atoms such as 1-methyl-2- (3-methylpentyl) cyclopropane;
Is exemplified.

Among hydrocarbon solvents having 4 to 10 carbon atoms, hydrocarbon solvents having 5 to 8 carbon atoms are industrially preferable. In addition, it is also preferable to use a mixture of these for the preparation of the catalyst solution so as to facilitate industrial use.

[Olefin]
In the method for producing an olefin polymer according to the present invention, an olefin having 2 or more carbon atoms is used as a raw material for the olefin polymer. The said olefin may be used individually by 1 type, and may use 2 or more types together.

The olefin is an olefin having 2 or more carbon atoms, preferably 3 to 20, more preferably 3 to 10. Further, the olefin is preferably an α-olefin, more preferably a linear or branched α-olefin.

Examples of the olefin include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, -Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene. Of these, propylene is particularly preferred.

In the present invention, as a raw material for the olefin polymer, together with the olefin,
Cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene;
Polar monomers, for example, α, such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid anhydride β-unsaturated carboxylic acid; metal salt such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt of α, β-unsaturated carboxylic acid; methyl acrylate, n-butyl acrylate, acrylic N-propyl acid, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-n-butylhexyl acrylate, methyl methacrylate, n-butyl methacrylate, n-propyl methacrylate, Α, β-unsaturation such as isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Vinyl esters such as rubonic acid ester; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate Unsaturated glycidyl etc. may be used.

Vinylcyclohexane, diene, polyene; aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, on-butylstyrene, mn Mono- or polyalkyl styrene such as butyl styrene, pn-butyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chlorostyrene, p-chlorostyrene, Polymerization can also proceed by coexisting a functional group-containing styrene derivative such as divinylbenzene; 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like in the reaction system.

In a preferred embodiment of the present invention, propylene is used for at least a part of the olefin. For example, the proportion of propylene used is preferably 60 to 100 mol% and more preferably 70 to 100 mol% with respect to 100 mol% of the olefin. Further, in the obtained polymer, the content ratio of the structural unit derived from propylene measured by ¹³ C-NMR is preferably 60 to 100 mol%, and more preferably 70 to 100 mol%. .

[Olefin polymer production conditions]
In the method for producing an olefin polymer according to the present invention, the polymerization temperature is not particularly limited, and is usually −100 to 250 ° C., preferably 40 to 200 ° C., more preferably 45 to 150 ° C., and particularly preferably 50. It is ˜150 ° C. (in other words, it is particularly preferably a temperature that can be industrialized). The polymerization pressure is usually in the range of normal pressure to 10 MPa-G (gauge pressure), preferably normal pressure to 5 MPa-G. When at least a part of the olefin is propylene, the polymerization temperature is preferably 50 ° C. or more, and particularly preferably 60 to 150 ° C. from the viewpoint of productivity.

Further, the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

The melting point of the olefin polymer can be adjusted by changing the polymerization temperature. The molecular weight of the olefin polymer can be adjusted by allowing hydrogen to exist in the polymerization reaction system or changing the polymerization temperature. Furthermore, the molecular weight of the olefin polymer can be adjusted by the amount of the compound (B) used as a component of the olefin polymerization catalyst. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

In the method for producing an olefin polymer according to the present invention, at the time of polymerization, the usage and order of addition of each component of the olefin polymerization catalyst such as the crosslinked metallocene compound (A) and the compound (B) are arbitrarily selected. The following method is exemplified.

(1) A method in which the bridged metallocene compound (A) and the compound (B) are added to the polymerization vessel in an arbitrary order; (2) a catalyst component in which the bridged metallocene compound (A) is supported on the carrier (C), and a compound ( A method of adding B) to the polymerization vessel in an arbitrary order; (3) a catalyst component in which the compound (B) is supported on the carrier (C), and the bridged metallocene compound (A) are added to the polymerization vessel in an arbitrary order. Method; (4) A method in which a catalyst component in which a bridged metallocene compound (A) and a compound (B) are supported on a carrier (C) is added to a polymerization vessel.

In each of the above methods (1) to (4), the catalyst component can be used after being dissolved in a solvent. As the solvent, generally, a hydrocarbon solvent having 4 to 10 carbon atoms can be used as described above. In the present invention, as described above, a high concentration catalyst solution (solvent: hydrocarbon solvent) of the bridged metallocene compound (A) can be prepared. From the viewpoint of polymerization activity, it is preferable to supply a catalyst solution having a bridged metallocene compound (A) concentration of 0.03 mmol / L to 2.0 mol / L to the polymerization system, more preferably 0.04 mmol / L to 1.. 5 mol / L, more preferably 0.05 mmol / L to 1.0 mol / L.

When a high concentration catalyst solution of the bridged metallocene compound (A) is used, the time until the catalyst solution is supplied to the polymerization system after preparation of the catalyst solution (hereinafter also referred to as “holding time”) is set long. Even so, high polymerization activity is exhibited. This is because when the concentration of the catalyst solution is high, the influence of poisoning and deactivation from the solvent is small. For example, the holding time can be normally set to 120 hours or shorter, preferably 36 hours or shorter.

On the other hand, when supplying a catalyst solution having a concentration of the bridged metallocene compound (A) of less than 0.03 mmol / L to the polymerization system, the retention time is set to 24 hours or less in order to suppress poisoning and deactivation from the solvent. It is preferable to set it to 12 hours or less.

Further, in each of the above methods (1) to (3), when the bridged metallocene compound (A) is dissolved in the solvent, or the catalyst component in which the bridged metallocene compound (A) is supported on the carrier (C) is dissolved in the solvent. More preferably, the compound (B) is not dissolved simultaneously.

In each of the above methods (1) to (4), at least two of the catalyst components may be contacted in advance. In each of the above methods (3) and (4) in which the compound (B) is supported on the carrier (C), the unsupported compound (B) is added to the polymerization vessel in any order as necessary. May be. In this case, the compound (B) supported on the carrier (C) and the compound (B) not supported may be the same or different.

The solid catalyst component in which the crosslinked metallocene compound (A) is supported on the support (C) and the solid catalyst component in which the crosslinked metallocene compound (A) and the compound (B) are supported on the support (C) It may be polymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

In the method for producing an olefin polymer according to the present invention, an olefin polymer is obtained by homopolymerizing or copolymerizing one or more of the olefins in the presence of the olefin polymerization catalyst. In the present invention, the polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization; and gas phase polymerization methods.

Inert hydrocarbon solvents used in the liquid phase polymerization method, that is, polymerization solvents include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclo Examples include alicyclic hydrocarbons such as pentane; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. Moreover, these inert hydrocarbon solvents may be used individually by 1 type, and may use 2 or more types together. Moreover, the olefin itself used as a raw material of an olefin polymer can also be used as a solvent.

[Olefin polymer]
According to the present invention described above, when an olefin such as propylene is polymerized, the olefin having a high melting point and a high molecular weight is efficiently produced with a high polymerization activity not only at a low polymerization temperature but also at a high polymerization temperature. A polymer can be produced.

The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of the olefin polymer is usually 90,000 or more, preferably 97,000 to 1,000,000, more preferably 110,000 to 1,000,000. The propylene polymer has an MWD (weight average molecular weight (Mw) / number average molecular weight (Mn)) of usually 1 to 3, preferably 1 to 2.9, more preferably 1 to 2.8.

The bridged metallocene compound (A) used in the present invention exhibits properties as a so-called single site catalyst and is advantageous for obtaining a polymer having a narrow molecular weight distribution as described above. Of course, a polymer having a wide molecular weight distribution can be obtained by adopting a so-called multistage polymerization method in which polymerization reactions under different conditions are sequentially performed.

The intrinsic viscosity [η] of the olefin polymer is preferably 1.20 dl / g or more, more preferably 1.25 dl / g or more, and further preferably 1.35 dl / g or more. The upper limit of the intrinsic viscosity [η] is usually about 10 dl / g.

A propylene polymer having an intrinsic viscosity [η] that is an index of weight average molecular weight (Mw) and molecular weight is in the above range is excellent in stability during melt extrusion.

Hereinafter, physical properties of the propylene polymer in the case of a propylene homopolymer or a copolymer of propylene and an olefin other than propylene (when at least a part of the olefin is propylene) will be described.

The melting point (Tm) determined by a differential scanning calorimeter (DSC) of the propylene polymer is usually 135 ° C. or higher, preferably 140 to 170 ° C., more preferably 145 to 170 ° C. A propylene polymer having a melting point (Tm) in the above range is excellent in moldability.

The crystallization temperature (Tc) determined by DSC of the propylene polymer is usually 70 ° C. or higher, more preferably 80 to 150 ° C., and more preferably 85 to 130 ° C. A propylene polymer having a crystallization temperature (Tc) in the above range is excellent in moldability.

When a plurality of crystal melting peaks are observed in the propylene polymer (for example, the low temperature side peak Tm1 and the high temperature side peak Tm2), the high temperature side peak is defined as the melting point (Tm) of the propylene polymer.

In the present invention, the weight average molecular weight (Mw), number average molecular weight (Mn), intrinsic viscosity [η], melting point (Tm) and crystallization temperature (Tc) of the olefin polymer are as described in the examples. The value to be measured.

Generally, when the polymerization temperature during olefin polymerization is increased, the melting point and molecular weight of the olefin polymer are decreased. According to the olefin polymerization catalyst, an olefin polymer having a melting point (Tm) of 145 ° C. or higher and a weight average molecular weight (Mw) of 97,000 or higher can be obtained with high polymerization activity even at an industrializable temperature. It can be manufactured efficiently.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. First, a method for measuring physical properties and properties of an olefin polymer will be described.

[Melting point (Tm), crystallization temperature (Tc)]
The melting point (Tm) or crystallization temperature (Tc) of the olefin polymer was measured as follows using DSC Pyris 1 or DSC 7 manufactured by PerkinElmer.

Under a nitrogen atmosphere (20 mL / min), the sample (about 5 mg) was (1) heated to 230 ° C. and held at 230 ° C. for 10 minutes, and (2) cooled to 30 ° C. at 10 ° C./min. After holding for 1 minute, (3) the temperature was raised to 230 ° C. at 10 ° C./min. The melting point (Tm) was calculated from the peak vertex of the crystal melting peak in the temperature raising process (3), and the crystallization temperature (Tc) was calculated from the peak vertex of the crystallization peak in the temperature lowering process (2).

In the olefin polymers described in Examples and Comparative Examples, when a plurality of crystal melting peaks are observed (for example, the low temperature side peak Tm1 and the high temperature side peak Tm2), the high temperature side peak is regarded as the melting point of the olefin polymer. (Tm).

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the olefin polymer is a value measured at 135 ° C. using a decalin solvent. That is, granulated pellets of olefin polymer (about 20 mg) are dissolved in decalin solvent (15 mL), and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After decalin solvent (5 mL) is added to the decalin solution for dilution, the specific viscosity ηsp is measured in the same manner as described above. This dilution operation of adding a decalin solvent (5 ml) was repeated twice more, and the value of ηsp / C when the concentration (C) of the olefin polymer was extrapolated to 0 was defined as the intrinsic viscosity [η] of the olefin polymer. did.

Intrinsic viscosity [η] = lim (ηsp / C) (C → 0)
[Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn; MWD) were measured using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters as follows. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is oji Chlorobenzene (Wako Pure Chemical Industries) and 0.025 wt% BHT (Takeda Pharmaceutical) as the antioxidant were used, the mobile phase was moved at 1.0 mL / min, the sample concentration was 15 mg / 10 mL, and the sample injection volume was 500 micron. A differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ . The molecular weight distribution and various average molecular weights were calculated as polypropylene molecular weights according to the general calibration procedure.

(Identification of target)
The structure of the compound obtained in the synthesis example was determined using 270 MHz ¹ H-NMR (JEOL GSH-270) and FD-MS (JEOL SX-102A).

[Bridged metallocene compound used in Comparative Example]
The bridged metallocene compound used in the comparative example was synthesized by the method described in the following patent publication. JP2000-212194, JP2004-168744, JP2004-189666, JP2004-161957, JP2007-302854, JP2007-302853, WO01 / 027124 pamphlet.

Synthesis Example 1 Catalyst (a): Synthesis of benzyl (phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

(I) Synthesis of 2,7-dibromo- 3,6-ditert-butylfluorene In a nitrogen stream, 170 mL of propylene carbonate was added to 15.22 g (54.7 mmol) of 3,6-ditert-butylfluorene and stirred. went. To this solution, 20.52 g (115 mmol) of N-bromosuccinimide was added. Stirring was performed at 80 ° C. for 5 hours. After natural cooling, the reaction solution was added to 800 mL of water. The mixture was stirred at room temperature for 15 minutes and filtered using a Kiriyama funnel. The obtained white yellow powder was washed 5 times with 10 mL of ethanol. A mixed solution of hexane and a small amount of dichloromethane was added to the powder and heated to 60 ° C. to dissolve all the powder. This solution was allowed to stand at −20 ° C. overnight. The precipitated crystals were washed 3 times with 5 mL of hexane to obtain the desired product as a white yellow powder (yield 21.16 g, yield 76%).
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ (ppm) 1.60 (18H), 3.75 (2H), 7.73 (2H), 7.81 (2H).
MS (FD): M / z 436 (M ^<+> ).
(Ii) Synthesis of 2,7-diphenyl-3,6 -ditert-butylfluorene In a 300 mL three-necked flask under a nitrogen atmosphere, 8.15 g of 2,7-dibromo-3,6-ditert-butylfluorene ( 18.7 mmol), 1.08 g (0.93 mmol) of Pd (PPh ₃ ), and 120 mL of dehydrated 1,2-dimethoxyethane were added, and the mixture was stirred at room temperature for 20 minutes. To this solution, 20 mL of an ethanol solution of 5.01 g (41.1 mmol) of phenylboric acid was added and stirred at room temperature for 20 minutes, and then 37.4 mL (74.8 mmol) of a 2.0 M aqueous sodium carbonate solution was added. Thereafter, the mixture was heated to reflux for 18 hours, allowed to cool naturally, and then quenched with dilute hydrochloric acid in an ice bath. Ether was added to extract the soluble part, and the organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and twice with a saturated saline solution, and then dried over magnesium sulfate. After the solvent was distilled off, the obtained solid was separated by column chromatography to obtain the desired product (yield 4.36 g, yield 54%).
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ (ppm) 1.29 (18H), 3.78 (2H), 7.16 (2H), 7.34 (10H), 7.97 ( 2H).
MS (FD): M / z 430 (M ^<+> ).
(Iii) Synthesis of 6-benzyl-6- phenylfulvene Under a nitrogen atmosphere, 2.45 g (25.7 mmol) of anhydrous magnesium chloride and 20 mL of dehydrated THF were added to a 100 mL Schlenk flask and stirred. To this mixed solution, 10.6 mL (21.2 mmol) of a 2.0 M sodium cyclopentadienide THF solution was added. Thereafter, the mixture was heated to reflux for 1 hour, and the resulting pink slurry was cooled in an ice bath. Then, a solution of 3.5 g (17.8 mmol) of benzyl phenyl ketone in 15 mL of dehydrated THF was added. The mixture was then stirred at room temperature for 18 hours, and the resulting orange solution was quenched with dilute hydrochloric acid aqueous solution. 30 mL of diethyl ether was added to extract soluble components, and the organic layer was neutralized and washed with a saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography to obtain the desired product as a reddish orange solid (yield 2.7 g, yield 62%).
¹ H-NMR (270 MHz, CDCl ₃ , TMS): δ (ppm) 4.2 (2H), 6.15-6.75 (4H), 7.08-7.30 (10H).
MS (GC): M / z 244 (M ^<+> ).
(Iv) Synthesis of benzyl (phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) Under a nitrogen stream, 2,7-diphenyl-3,6-ditert- To 4.02 g (9.3 mmol) of butylfluorene, 40 mL of anhydrous THF was added and stirred / dissolved. After cooling in an ice bath, 6.2 mL (10.1 mmol) of 1.63 M n-butyllithium hexane solution was added. After stirring at room temperature for 2.5 hours, the resulting deep red solution was cooled in a dry ice / methanol bath, and 2.7 g (11.1 mmol) of 6-benzyl-6-phenylfulvene in THF (15 mL) Was added. The mixture was stirred for 16 hours while gradually warming to room temperature, and then the resulting deep red solution was added with dilute hydrochloric acid in an ice bath to terminate the reaction. Diethyl ether was added to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with diethyl ether and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, and once with saturated brine, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography to obtain the desired product as a pale yellow powder (yield 2.3 g, yield 36.9%).
¹ H-NMR (270 MHz, CDCl ₃ ): δ (ppm) 1.21-1.31 (18H), 2.53-2.82 (2H), 3.42-3.78 (2H), 4. 83 (1H), 5.84-6.10 (3H), 6.75-7.31 (22H), 7.63-7.70 (2H).
(V) Synthesis of benzyl (phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride Into a 100 mL Schlenk tube under a nitrogen atmosphere, benzyl (phenyl ) 0.81 g (1.20 mmol) of methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) and 40 mL of anhydrous diethyl ether were added and stirred / dissolved. The solution was cooled in an ice bath, 1.60 mL (2.61 mmol) of a 1.63 M n-butyllithium hexane solution was added, and the mixture was stirred for 4 hours while maintaining the ice temperature. The obtained orange slurry was cooled in a dry ice / methanol bath, and 0.30 g (1.29 mmol) of anhydrous zirconium tetrachloride was added. Thereafter, the mixture was stirred for 17 hours while gradually warming to room temperature to obtain a reddish brown suspension.

After the solvent was dried under reduced pressure, dichloromethane extraction was performed in a glove box, and further pentane extraction was performed from the dichloromethane distilled off. After pentane was distilled off under reduced pressure, the residue was further dried under reduced pressure to obtain the desired product as an orange powder (yield 0.49 g, yield 48.9%).
¹ H-NMR (270 MHz, CDCl ₃ ): δ (ppm) 1.19-1.25 (18H), 3.74-4.49 (2H), 5.37-6.45 (4H), 6. 65-7.53 (22H), 8.22-8.29 (2H).
MS (FD): M / Z 834 (M ⁺ )
In a nitrogen atmosphere, 10 mg of this catalyst (a) was placed in a sample bottle and dissolved by adding n-hexane while stirring at 25 ° C., and the solubility determined from the amount of n-hexane required was 1.005 mmol / L. there were.

Synthesis Example 2 Catalyst (b): benzyl (phenyl) methylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

(I) Synthesis of benzyl (phenyl) methylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-ditert-butylfluorene) 3,6-ditert-butyl- under a nitrogen stream 200 mL of anhydrous THF was added to 2.15 g (4.3 mmol) of 2,7-di-p-chlorophenylfluorene and stirred / dissolved. After cooling in an ice bath, 2.96 mL of a 1.63 M n-butyllithium hexane solution ( 4.7 mmol) was added. After stirring at room temperature for 1.5 hours, the resulting deep red solution was cooled in a dry ice / methanol bath and a solution of 1.26 g (5.2 mmol) of 6-benzyl-6-phenylfulvene in THF (50 mL) was added. did. After stirring for 4 hours while gradually warming to room temperature, the obtained solution was diluted with dilute hydrochloric acid in an ice bath to terminate the reaction. After diethyl ether was added for liquid separation, the aqueous layer was extracted twice with diethyl ether and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain the desired product (yield 1.8 g, yield 56%).
¹ H-NMR (270 MHz, CDCl ₃ ): δ (ppm) 1.21-1.31 (18H), 2.53-2.82 (2H), 3.42-3.78 (2H), 4. 83 (1H), 5.84-6.10 (3H), 6.75-7.31 (20H), 7.63-7.70 (2H).
(Ii) Synthesis of benzyl (phenyl) methylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-ditert-butylfluorenyl) zirconium dichloride Into a 100 mL Schlenk tube under a nitrogen atmosphere Add 0.99 g (1.33 mmol) of benzyl (phenyl) methylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-ditert-butylfluorene) and 50 mL of anhydrous diethyl ether and stir / Dissolved. This solution was cooled in an ice bath, 1.71 mL (2.79 mmol) of a 1.63-M n-butyllithium hexane solution was added, and the mixture was stirred at ice temperature for 4 hours. The obtained orange slurry was cooled in a dry ice / methanol bath, and 0.31 g (1.33 mmol) of anhydrous zirconium tetrachloride was added. Thereafter, the mixture was stirred for 17 hours while gradually warming to room temperature to obtain a reddish brown suspension.

After the solvent was dried under reduced pressure, dichloromethane extraction was performed in the glove box, and dichloromethane was distilled away, washed with pentane, and dried under reduced pressure to obtain the desired product (yield 0.90 g, yield 69.3%). ).
¹ H-NMR (270 MHz, CDCl ₃ ): δ (ppm) 1.19-1.25 (18H), 3.74-4.49 (2H), 5.37-6.45 (4H), 6. 65-7.53 (20H), 8.22-8.29 (2H).
MS (FD): M / Z 834 (M ⁺ )
Under a nitrogen atmosphere, 10 mg of this catalyst (b) was placed in a sample bottle and dissolved by adding n-hexane while stirring at 25 ° C., and the solubility determined from the amount of n-hexane required was 4.098 mmol / L. there were.

Synthesis Example 3 Catalyst (c): benzyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

(I) Synthesis of 6-benzyl-6- (p-chlorophenyl) fulvene Under a nitrogen atmosphere, 2.45 g (25.7 mmol) of anhydrous magnesium chloride and 20 mL of dehydrated THF were added to a 100 mL Schlenk flask and stirred. To this mixed solution, 10.6 mL (21.2 mmol) of a 2.0 mol / L sodium cyclopentadienide THF solution was added. The mixture was then heated to reflux for 1 hour. The resulting pink slurry was cooled in an ice bath, and a solution of 3.5 g (17.8 mmol) of benzyl (p-chlorophenyl) ketone in 15 mL of dehydrated THF was added. The mixture was then stirred at room temperature for 18 hours, and the resulting orange solution was quenched with dilute aqueous hydrochloric acid. 30 mL of diethyl ether was added to extract soluble components, and the organic phase was neutralized and washed with a saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography to obtain the desired product as a red-orange solid, which was directly used in the next step (yield 2.7 g).

(Ii) Synthesis of benzyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) Under a nitrogen stream, 3,6-ditert-butyl-2, To 4.3 g (10 mmol) of 7-diphenylfluorene, 200 mL of anhydrous THF was added and stirred / dissolved. After cooling in an ice bath, 11 mL (6.74 mmol) of a hexane solution of 1.63 M n-butyllithium was added. After stirring at room temperature for 1.5 hours, the resulting deep red solution was cooled in a dry ice / methanol bath and a solution of 6.34 g (12 mmol) of 6-benzyl-6- (p-chlorophenyl) fulvene in THF (50 mL). Was added. After stirring for 4 hours while gradually warming to room temperature, the obtained solution was diluted with dilute hydrochloric acid in an ice bath to terminate the reaction. After diethyl ether was added for liquid separation, the aqueous layer was extracted twice with diethyl ether and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain the desired product (yield 5.2 g, yield 73%).
¹ H-NMR (270 MHz, CDCl ₃ ): δ (ppm) 1.21-1.31 (18H), 2.53-2.82 (2H), 3.42-3.78 (2H), 4. 83 (1H), 5.84-6.10 (3H), 6.75-7.31 (19H), 7.63-7.70 (2H).
(Iii) Synthesis of benzyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride In a nitrogen atmosphere, add benzyl ( 2.7 g (3.81 mmol) of p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) and 50 mL of anhydrous diethyl ether were added and stirred / dissolved. The solution was cooled in an ice bath, 5.12 mL (7.99 mmol) of a 1.63-M n-butyllithium hexane solution was added, and the mixture was stirred for 4 hours while maintaining the ice temperature. The resulting orange slurry was cooled in a dry ice / methanol bath, and 0.85 g (3.64 mmol) of anhydrous zirconium tetrachloride was added. Thereafter, the mixture was stirred for 17 hours while gradually warming to room temperature to obtain a reddish brown suspension.

After the solvent was dried under reduced pressure, dichloromethane extraction was performed in the glove box, and dichloromethane was distilled away, washed with pentane, and dried under reduced pressure to obtain the desired product (yield 1.2 g, yield 36%).
¹ H-NMR (270 MHz, CDCl ₃ ): δ (ppm) 1.19-1.25 (18H), 3.74-4.49 (2H), 5.37-6.45 (4H), 6. 65-7.53 (20H), 8.22-8.29 (2H).
MS (FD): M / Z 834 (M ⁺ )
Under a nitrogen atmosphere, 10 mg of this catalyst (c) was placed in a sample bottle and dissolved by adding n-hexane while stirring at 25 ° C., and the solubility determined from the amount of n-hexane required was 1.585 mmol / L. there were.

Synthesis Example 4 Catalyst (d): benzyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

(I) Synthesis of benzyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-ditert-butylfluorene) 3,6-ditert- To 1.53 g (3.06 mmol) of butyl-2,7-di-p-chlorophenylfluorene, 40 mL of toluene and 3.5 g of THF were added and stirred / dissolved. After cooling in an ice bath, 1.67 M of n-butyllithium was added. 2 mL (3.3 mmol) of hexane solution was added. After stirring at room temperature for 1.5 hours, the resulting deep red solution was cooled in a dry ice / methanol bath and 1.1 g (3.95 mmol) of 6-benzyl-6- (p-chlorophenyl) fulvene was added. The mixture was stirred for 19 hours while gradually warming to room temperature, and the resulting solution was added with dilute hydrochloric acid in an ice bath to terminate the reaction. After diethyl ether was added for liquid separation, the aqueous layer was extracted twice with diethyl ether and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water and once with a saturated saline solution, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain the desired product (yield 1.0 g).

(Ii) Synthesis of benzyl (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-ditert-butylfluorenyl) zirconium dichloride Under nitrogen atmosphere, benzyl (p -Chlorophenyl) methylene (cyclopentadienyl) (2,7-di-p-chlorophenyl-3,6-ditert-butylfluorene) 600 mg (0.77 mmol) and anhydrous diethyl ether 40 mL were added and stirred / dissolved. This solution was cooled in an ice bath, 0.96 mL (1.62 mmol) of a 1.67M n-butyllithium hexane solution was added, and the mixture was stirred for 4 hours while maintaining the ice temperature. The resulting orange slurry was cooled in a dry ice / methanol bath, and 170 mg (0.73 mmol) of anhydrous zirconium tetrachloride was added. Thereafter, the mixture was stirred for 17 hours while gradually warming to room temperature to obtain a reddish brown suspension.

After the solvent was dried under reduced pressure, hexane extraction was carried out in the glove box, and the evaporated product was washed with pentane and dried under reduced pressure to obtain the desired product (yield 350 mg).
¹ H-NMR (270 MHz, CDCl ₃ ): δ (ppm) 1.19-1.25 (18H), 3.74-4.49 (2H), 5.37-6.45 (4H), 6. 65-7.53 (19H), 8.22-8.29 (2H).
Under a nitrogen atmosphere, 10 mg of this catalyst (d) was placed in a sample bottle, and when n-hexane was added and dissolved while stirring at 25 ° C., the solubility determined from the amount of n-hexane required was 0.901 mmol / L. there were.

Synthesis Example 5 Catalyst (e): Methyl (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

(I) A solution of cyclopentadienyl lithium salt (5.9 g, 81.9 mmol) in dehydrated diethyl ether (100 mL) was cooled in an ice bath under a 6-methyl-6- (p-tolyl) fulvene nitrogen atmosphere. '-Methylacetophenone (10.0 g, 74.5 mmol) was added dropwise. Thereafter, the reaction was stirred for 20 hours at room temperature. After completion of the reaction, a dilute aqueous hydrochloric acid solution was added and the mixture was extracted with hexane. The organic layer was washed with water and then dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain a red liquid. Purification by column chromatography (silica gel, solvent: hexane) gave 9.8 g of 6-methyl-6- (p-tolyl) fulvene. Analytical values are shown below.
¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard): δ (ppm) 7.25 (2H), 7.12 (2H), 6.55 (1H), 6.51 (1H), 6.40 (1H), 6.15 (1H), 2.43 (3H), 2.30 (3H)
(Ii) Methyl (p-tolyl) cyclopentadienyl (2,7-diphenyl-3,6-ditert-butylfluorenyl) methane in a nitrogen atmosphere and 2,7-diphenyl-3,6-ditert- A hexane solution (6.3 ml, 10.2 mmol) of n-butyllithium was added dropwise to a solution of butylfluorene (4.0 g, 9.3 mmol) in dehydrated tetrahydrofuran (50 ml) at −10 ° C., and the mixture was stirred at room temperature for 20 hours. . Thereafter, 6-methyl-6- (p-tolyl) fulvene (1.9 g, 10.2 mmol) was added dropwise to the solution at −10 ° C., and the mixture was stirred at room temperature for 2 hours to be reacted. After completion of the reaction, a dilute aqueous hydrochloric acid solution was added and the mixture was extracted with hexane. The organic layer was washed with water and then dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain a light brown solid. The obtained solid was recrystallized from methanol to obtain 5.1 g of the desired product. Analytical values are shown below.
¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard): δ (ppm) 7.8 (2H), 6.90-7.35 (15H), 6.70, 6.6, 6.5, 6 .3, 6.15 (4H), 5.45, 5.3, 4.7 (2H), 2.95 to 2.7 (1H), 2.18 (3H), 1.3 to 1.21 (18H), 1.01 to 1.00 (3H)
FD-MS: m / z 612 (M ⁺ )
(Iii) Methyl (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6- ditert-butylfluorenyl ) zirconium dichloride under nitrogen atmosphere, methyl (p-tolyl) cyclopentadi N-Butyllithium solution in hexane (2.1 ml) to a solution of enyl (2,7-diphenyl-3,6-ditert-butylfluorenyl) methane (1.0 g, 1.63 mmol) in dehydrated diethyl ether (40 ml) 3.3 mmol) was slowly added dropwise, and the mixture was further stirred at room temperature for 24 hours. Thereafter, the mixture was cooled to −60 ° C., zirconium tetrachloride (0.38 g, 1.63 mmol) was added, and the mixture was stirred for 24 hours while gradually returning to room temperature. The resulting red suspension was filtered through celite to remove lithium chloride, concentrated, washed with diethyl ether, cooled with a hexane solution, and recovered. After collection, methyl (p-tolyl) methylene (cyclopentadienyl) 150 mg (red solid) of (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was obtained. Analytical values are shown below.
¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard): δ (ppm) 8.2 (2H), 6.9 to 7.5 (16H), 6.4 (1H), 6.23 (1H) 5.68 (1H), 5.55 (1H), 5.38 (1H), 2.25 (3H), 1.20, 1.25 (21H)
FD-MS: m / z 772 (M ⁺ )
In a nitrogen atmosphere, 10 mg of this catalyst (e) was placed in a sample bottle and dissolved by adding n-hexane while stirring at 25 ° C., and the solubility determined from the amount of n-hexane required was 6.221 mmol / L. there were.

Synthesis Example 6 Catalyst (f): n-octyl (phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

(I) Synthesis of 6- (n-octyl) -6 -phenylfulvene Under a nitrogen atmosphere, a 100 mL Schlenk flask was charged with 2.0 g (9.2 mmol) of n-nonanophenone and 30 mL of dehydrated THF to prepare a solution. Thereto was added 5.6 mL (11.2 mmol) of 2.0 M sodium cyclopentadienide THF solution under ice cooling, and the mixture was stirred at room temperature for 19 hours. The resulting dark red solution was diluted with dilute aqueous hydrochloric acid under ice cooling. Quenched. 30 mL of diethyl ether was added to extract soluble components, and the organic layer was neutralized and washed with a saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography to obtain the desired product as a red liquid (yield 1.77 g, yield 72.5%).

(Ii) Synthesis of n-octyl (phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) Under a nitrogen stream, 2,7-diphenyl-3,6-di Add 40 mL of anhydrous THF to 1.71 (3.97 mmol) of tert-butylfluorene, stir / dissolve, cool in an ice bath, and then add 2.8 mL (4.68 mmol) of 1.67M n-butyllithium hexane solution. did. After stirring for 2 hours under ice cooling, the resulting deep reddish brown solution was cooled with ice water, and a solution of 1.6 g (6.0 mmol) of 6- (n-octyl) -6-phenylfulvene in THF (30 mL) was obtained. ) Was added. The mixture was stirred for 16 hours while gradually warming to room temperature, and then the resulting brown solution was added with dilute hydrochloric acid in an ice bath to terminate the reaction. Diethyl ether was added to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with diethyl ether and combined with the previous organic layer. The extract was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, and once with saturated brine, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography to obtain the desired product as an ocherous viscous liquid (yield 1.49 g, yield 53.9%).

(Iii) Synthesis of n-octyl (phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride In a nitrogen atmosphere, n -0.70 g (1.00 mmol) of octyl (phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) and 40 mL of anhydrous diethyl ether were added and stirred / dissolved . This solution was cooled in an ice bath, 1.35 mL (2.25 mmol) of a 1.67 M n-butyllithium hexane solution was added, and the mixture was stirred at ice temperature for 3 hours and then at room temperature for 1.5 hours. The obtained orange slurry was cooled in a dry ice / methanol bath, and 0.26 g (1.12 mmol) of anhydrous zirconium tetrachloride was added. Thereafter, the mixture was stirred for 3 hours while gradually warming to room temperature to obtain an orange vermilion suspension.

After the solvent was dried under reduced pressure, dichloromethane extraction was performed in a glove box, and hexane extraction was further performed from the dichloromethane distilled off. After the hexane was distilled off under reduced pressure, the residue was further dried under reduced pressure to obtain the desired product as a red powder (yield 0.79 g, yield 91.6%).
¹ H-NMR (270 MHz, CDCl ₃ ): δ (ppm) 1.19-1.35 (33H), 2.34-2.78 (2H), 5.37-6.45 (4H), 6. 84-6.99 (5H), 7.02-7.47 (10H), 7.50 (2H), 8.22-8.27 (2H).
Under a nitrogen atmosphere, 10 mg of this catalyst (f) was placed in a sample bottle and dissolved by adding n-hexane while stirring at 25 ° C., and the solubility determined from the amount of n-hexane required was 7.683 mmol / L. there were.

Catalyst (g): Diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

In a nitrogen atmosphere, 10 mg of this catalyst (g) was taken into a sample bottle and dissolved by adding n-hexane while stirring at 25 ° C. Even when 30 mL of n-hexane was added, part of the catalyst remained undissolved. Therefore, the solubility is 0.211 mmol / L or less.

Catalyst (h): Dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride

In a nitrogen atmosphere, 10 mg of this catalyst (h) is taken into a sample bottle and dissolved by adding n-hexane while stirring at 25 ° C. Even when 30 mL of n-hexane is added, part of the catalyst remains undissolved. Therefore, the solubility is 0.278 mmol / L or less.

[Example 1]
In a SUS autoclave with an internal volume of 15 mL sufficiently purged with nitrogen, 0.4 mL (0.05 M, 20 μmol) of triisobutylaluminum and cyclohexane and hexane as a polymerization solvent were mixed in cyclohexane: hexane = 9: 1 (volume ratio). 2.7 mL of the solvent was added and stirred at 600 rpm. The solution was heated to 50 ° C. and then pressurized with propylene until the total pressure was 7 bar.

In a nitrogen atmosphere, 2.5 mg (molecular weight 835.07 g / mol) of the catalyst (a) as a crosslinked metallocene compound was placed in a Schlenk tube, dissolved in 5.5 mL of hexane, and then 0.36 mL of a suspension of modified methylaluminoxane ( n-Hexane solvent, 4.15M in terms of aluminum atom, 1.49mmol) was added at room temperature while stirring to prepare a catalyst solution having a catalyst (a) concentration of 0.00051M.

After maintaining the catalyst solution at room temperature and under a nitrogen atmosphere for 30 minutes, 0.2 mL (0.00051 M, 0.10 μmol) of the catalyst solution and cyclohexane and hexane as polymerization solvents in the autoclave were added to cyclohexane: hexane = 9. 1 (volume ratio) mixed solvent 0.7mL was added, temperature was heated up to 65 degreeC, and superposition | polymerization was started. After polymerization at 65 ° C. for 9 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. Methanol 50mL and a small amount of hydrochloric acid aqueous solution were added to the obtained polymer, and it stirred at room temperature for 1 hour. Thereafter, the polymer was filtered and dried under reduced pressure to obtain 0.60 g of syndiotactic polypropylene.

The polymerization activity was 39.90 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer was 1.48 dl / g, the weight average molecular weight (Mw) was 127,000, the number average molecular weight (Mn) was 65,000, the molecular weight distribution (Mw / Mn) was 1.96, crystals The conversion temperature (Tc) was 96.5 ° C., and the melting points (Tm1, Tm2) were 140.0 ° C. and 147.9 ° C., respectively.

[Examples 2 to 9]
In Example 1, it carried out like Example 1 except having changed the bridge | crosslinking metallocene compound used, its addition amount, the retention time after catalyst solution preparation, the polymerization temperature, and the polymerization time as shown in Table 18. The results are shown in Table 18. “Mixed” in Table 18 refers to a solvent in which cyclohexane and hexane are mixed in cyclohexane: hexane = 9: 1 (volume ratio).

As can be seen from Examples 5 and 6, in the example where the catalyst solution preparation concentration was as high as 0.500 mmol / L, high polymerization activity was exhibited regardless of the retention time after catalyst preparation. Further, as seen in Example 7, even in the case where the catalyst solution preparation concentration was as low as 0.020 mmol / L, it can be used practically by setting the retention time after catalyst preparation to a short time. Polymerization activity.

As described above, the bridged metallocene compound (A) used in the present invention is excellent in solubility in a hydrocarbon solvent, so that a catalyst solution can be prepared using a smaller amount of solvent. This is a useful performance expected to reduce the possibility of being affected by the lot of the solvent to be used, especially when commercializing the production of olefin polymers.

[Comparative Example 1]
In a SUS autoclave with an internal volume of 15 mL sufficiently purged with nitrogen, 0.4 mL (0.05 M, 20 μmol) of triisobutylaluminum and cyclohexane and hexane as a polymerization solvent were mixed in cyclohexane: hexane = 9: 1 (volume ratio). 2.7 mL of the solvent was added and stirred at 600 rpm. The solution was heated to 50 ° C. and then pressurized with propylene until the total pressure was 7 bar.

Under a nitrogen atmosphere, 3.0 mg (molecular weight 821.04 g / mol) of the catalyst (g) as a cross-linked metallocene compound was placed in a Schlenk tube, and 4.55 mL of dehydrated hexane was added and stirred for 5 minutes. Further, 0.95 mL of dehydrated hexane and 0.27 mL of a suspension of modified methylaluminoxane (n-hexane solvent, 2.96 M in terms of aluminum atom, 0.80 mmol) were added, and the mixture was stirred at room temperature for 15 minutes to obtain a catalyst solution. Was prepared.

After holding the catalyst solution at room temperature and under a nitrogen atmosphere for 30 minutes, 0.2 mL of the catalyst solution and 9: 1 (volume ratio) of cyclohexane and hexane as polymerization solvents were mixed in the autoclave. 7 mL was added and the temperature was raised to 65 ° C. to initiate polymerization. After polymerization at 65 ° C. for 10 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. Methanol 50mL and a small amount of hydrochloric acid aqueous solution were added to the obtained polymer, and it stirred at room temperature for 1 hour. Thereafter, the polymer was filtered and dried under reduced pressure to obtain 0.06 g of syndiotactic polypropylene.

Assuming that the concentration of the catalyst solution was 0.00050M, the polymerization activity was 3.00 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer was 2.81 dl / g, weight average molecular weight (Mw) was 293,000, number average molecular weight (Mn) was 134,000, molecular weight distribution (Mw / Mn) was 2.18, crystal The conversion temperature (Tc) was 96.9 ° C., and the melting points (Tm1, Tm2) were 137.6 ° C. and 144.1 ° C., respectively.

[Comparative Example 2]
Comparative Example 1 was carried out in the same manner as Comparative Example 1 except that the bridged metallocene compound used, the amount thereof added, the polymerization temperature and the polymerization time were changed as shown in Table 18. The results are shown in Table 18. “Mixed” in Table 18 refers to a solvent in which cyclohexane and hexane are mixed in cyclohexane: hexane = 9: 1 (volume ratio).

Claims (12)

1. (A) a bridged metallocene compound represented by the following general formula [1];
   (B) (b-1) an organoaluminum oxy compound,
   In the presence of an olefin polymerization catalyst comprising (b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and (b-3) at least one compound selected from organoaluminum compounds And at least one olefin selected from olefins having 2 or more carbon atoms, and a method for producing an olefin polymer:
   

   

   [In Formula [1],
   R ¹ to R ⁴ each independently represents a group selected from a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group and a silicon-containing group, and two adjacent groups are bonded to form a ring. May be;
   R ⁵ to R ⁹ each independently represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group and a silicon-containing group, and two adjacent groups are They may combine to form a ring;
   R ¹⁰ to R ¹² each independently represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a nitrogen-containing group, an oxygen-containing group and a silicon-containing group;
   Y represents a carbon atom or a silicon atom;
   M represents Ti, Zr or Hf;
   Q is a structure selected from a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair; j Represents an integer of 1 to 4, and when j is 2 or more, a plurality of Qs may be the same or different from each other. ]
2. In the general formula [1], R ¹ and R ⁴ are each independently a group selected from a hydrocarbon group having 1 to 40 carbon atoms and a halogen-containing hydrocarbon group having 1 to 40 carbon atoms, and R ² and R ³ 2. The method for producing an olefin polymer according to claim 1, wherein the one or more groups are a group selected from a hydrocarbon group having 1 to 40 carbon atoms and a silicon-containing group.
3. 2. The general formula [1], wherein R ¹ and R ⁴ are each independently a group selected from an aryl group having 6 to 20 carbon atoms and a halogen-containing aryl group having 6 to 20 carbon atoms. Or the manufacturing method of the olefin polymer of 2.
4. 2. The general formula [1], wherein R ¹² is a group selected from a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, and a halogen-containing hydrocarbon group having 1 to 40 carbon atoms. 2. The method for producing an olefin polymer according to 2.
5. In the general formula [1], R ¹⁰ to R ¹¹ are all hydrogen atoms, R ¹² contains an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a halogen having 6 to 20 carbon atoms. 3. The method for producing an olefin polymer according to claim 1, wherein the olefin polymer is a group selected from aryl groups, or R ¹⁰ to R ¹² are all hydrogen atoms.
6. 3. The general formula [1], wherein R ⁵ to R ⁹ are each independently a group selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms. A method for producing an olefin polymer.
7. The method for producing an olefin polymer according to claim 1 or 2, wherein the olefin polymerization catalyst further contains a carrier (C).
8. 3. The method for producing an olefin polymer according to claim 1, wherein at least a part of the olefin is propylene.
9. The olefin polymer production according to claim 1 or 2, wherein the solubility of the bridged metallocene compound represented by the general formula [1] in n-hexane at 25 ° C is 0.5 mmol / L or more. Method.
10. The olefin weight according to claim 1 or 2, wherein a solution having a concentration of the bridged metallocene compound represented by the general formula [1] of 0.05 mmol / L to 1.0 mol / L is supplied to the polymerization system. Manufacturing method of coalescence.
11. The method for producing an olefin polymer according to claim 1 or 2, wherein the polymerization temperature is 50 to 150 ° C.
12. Melting point (Tm) measured by a differential scanning calorimeter of the resulting propylene polymer when the polymerization temperature is 50 to 150 ° C. (if multiple crystal melting peaks are observed, the melting point based on the high temperature side peak (Tm) ) Is 145 to 170 ° C., the intrinsic viscosity ([η]) measured in decalin at 135 ° C. is 1.25 dl / g or more, and the weight average molecular weight (Mw) measured by gel permeation chromatography is 3. The propylene polymer according to claim 1, wherein the propylene polymer is 97,000 or more and has a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of 1 to 3. Manufacturing method.